Use of phenethyl acrylamides, novel phenethyl acrylamides, method for the production thereof and agents containing the same

ABSTRACT

The invention relates to the use of phenethyl acrylamides of formula I for controlling phytopathogenic fungi, wherein the substituents of said phenethyl acrylamides have the following significations: X signifies halogen, alkyl, halogenalkyl, alkoxy halogenalkoxy and —O—C(R a , R b )—C≡C—R 6 ; R a , R b  and R c  have the signification given in the description; m, n independently signify 1 to 4, the radicals X or Y being potentially different if m or n is higher than 1; Y signifies halogen, nitro, cyano, alkyl, CF 3 , alkoxy and phenyl; R 1 , R 2  independently signify hydrogen, halogen, alkyl, alkoxy, halogenalkoxy and CF 3 ; R 3 , R 4 , R 5 , and R 6  independently signify hydrogen, alkyl and alkoxy, or R 3  and R 4  together form a cyclopropyl ring, whereby the C—R 5  and C—R 6  bonds can be in position E or Z in relation to each other. The invention also relates to novel phenethyl acrylamides, a method for the productio thereof, and agents containing the same.

[0001] The present invention relates to the use of phenethylacrylamidesof the formula I

[0002] in which the substituents have the following meanings:

[0003] X is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy,C_(l)-C₄-haloalkoxy and —O—C(R^(a),R^(b))—C≡C—R⁶;

[0004] R^(a),R^(b) independently of one another are hydrogen andC₁-C₆-alkyl;

[0005] R^(c) is hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl and phenyl whichcan be substituted by halogen, cyano, nitro, CF₃, C₁-C₄-alkyl and/orC₁-C₄-alkoxy;

[0006] m,n independently of one another are 1 to 4, it being possiblefor the radicals X and Y to be different if m or n is greater than 1;

[0007] Y is halogen, nitro, cyano, C₁-C₄-alkyl, CF₃, C₁-C₄-alkoxy andphenyl;

[0008] R¹, R² independently of one another are hydrogen, halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and CF₃;

[0009] R³,R⁴,R⁵,R⁶ independently of one another are hydrogen,C₁-C₄-alkyl and C₁-C₄-alkoxy or

[0010] R³ and R⁴ together form a cyclopropyl ring, it being possible forthe C—R⁵— and C—R⁶-bonds to be in the E- or Z-position relative to eachother;

[0011] for controlling phytopathogenic fungal pests.

[0012] The invention furthermore relates to novel phenethylacrylamides,to processes for their preparation, and to compositions comprising them.

[0013] Various arylacrylamides are disclosed in EP-A 407 217, EP-A 529736, WO-A 93/01523, JP-A 06/080 616, U.S. Pat. No. 3,657,340, U.S. Pat.No. 3,526,653 and JP-A 63/154 649. Some of them are described asherbicides. However, their fungicidal action is unknown in the priorart.

[0014] α-Oximinophenylacetic acid arylamides are described in WO-A96/17825 and WO-A 96/23763 as fungicides and in JP 02/200 658 asherbicides. In WO-A 96/17825, arylacrylamides are only covered by thegeneral disclosure.

[0015] However, the fungicidal action of the [lacuna] described in theabovementioned documents is not satisfactory in many cases. It istherefore an object of the invention to find compounds with an improvedaction.

[0016] It has been found that this object is achieved by the use of thephenylethylacrylamides of the Formula I as fungicides and the novelphenethylacrylamides, and compositions comprising them.

[0017] The phenethylacrylamides of the formula I can be prepared by thesynthetic routes described in EP-A 407 217, EP-A 529 736, WO-A 93/01523,JP-A 06/080 616, U.S. Pat. No. 3,657,340, U.S. Pat. No. 3,526,653 andJP-A 63/154 649 whose disclosure is herewith incorporated.

[0018] The novel phenethylacrylamides in which R¹ and R² are identicaland are Cl, F and CH₃ can be obtained, for example, starting from α-ketoesters of the formula II where R is C₁-C₄-alkyl by the routes describedhereinbelow:

[0019] Compounds in which R¹ and R² are chlorine are obtained byreacting α-keto esters of the formula II with triphenylphosphine (PPh₃)and CCl₄ to give acrylic esters of the formula IIIa. This reaction isusually carried out at temperatures from 10° C. to 120° C., preferably20° C. to 80° C., in an inert organic solvent [cf. tetrahedron Lett., p.3003 et seq., 1988].

[0020] Suitable solvents are aromatic hydrocarbons such as toluene, o-,m- and p-xylene, halogenated hydrocarbons such as methylene chloride,chloroform, and chlorobenzene, nitriles such as acetonitrile andpropionitrile, and dimethyl sulfoxide, dimethyl formamide and dimethylacetamide, especially preferably acetonitrile and propionitrile.Mixtures of these may also be used.

[0021] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ CCl₄and PPh₃ in excess based on II.

[0022] Compounds in which R¹ and R² are fluorine are obtained byreacting α-keto esters of the formula II withdiphenyl-1,1-difluoromethylphosphine of the formula VI where Ph isphenyl, to give acrylic esters of the formula IIIb. This reaction isusually carried out at temperatures from −70° C. to +80° C., preferably0° C. to 20° C., in an inert organic solvent in the presence of a base[cf. tetrahedron Lett., p. 5571 et seq., 1990].

[0023] Suitable solvents are ethers such as diethyl ether, diisopropylether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran,especially preferably diethyl ether and tetrahydrofuran. Mixtures ofthese may also be used.

[0024] Suitable bases are, generally, inorganic compounds such as alkalimetal hydrides and alkaline earth metal hydrides such as lithiumhydride, sodium hydride, potassium hydride and calcium hydride, alkalimetal amides such as lithium amide, sodium amide and potassium amide,organo metal compounds, in particular alkali metal alkyls such asmethyllithium, butyllithium, lithiumdiisopropylamine (LDA) andphenyllithium. Butyllithium and LDA are especially preferred.

[0025] In general, the bases are employed in catalytic amounts, and theymay also be used in equimolar amounts, in excess or, if appropriate, assolvents.

[0026] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ VI inan excess based on II.

[0027] Alternatively, compounds in which R¹ and R² are fluorine, mayalso be obtained by reacting α-keto esters of the formula II with sodium2-chloro-2,2-difluoroacetate, of the formula VII, and triphenylphosphine(PPh₃) to give acrylic esters of the formula IIIb. This reaction isusually carried out at temperatures from 20° C. to 180° C., preferably60° C. to 180° C., in an inert organic solvent [cf. Org. Synth. Vol. V,p. 949 et seq. (1973)].

[0028] Suitable solvents are aromatic hydrocarbons such as toluene, o-,m- and p-xylene, ethers such as diethyl ether, diisopropyl ether,tert-butyl methyl ether, dioxane, anisole, tetrahydrofuran (THF),ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and1,2-diethoxyethane, nitrites such as acetonitrile and propionitrile, andalso dimethyl sulfoxide, dimethylformamide and dimethylacetamide,especially preferably THF and diethylene glycol dimethyl ether. Mixturesof these may also be used.

[0029] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ VII inan excess based on II.

[0030] Compounds in which R¹ and R² are methyl are obtained by reactingα-keto esters of the formula II with iso-propylphosphonium halide of theformula VIII in the sense of a Wittig reaction. Preferred as halides ofthe formula VIII are iodides and bromides.

[0031] In the above reaction scheme, {circle over (P)} in the formulaVIII is a phosphoranyl radical, such as, for example,triphenylphosphoranyl.

[0032] The Wittig reaction is usually carried out at temperatures from−78° C. to +85° C., preferably −10° C. to +65° C., in an inert organicsolvent in the presence of a base [cf. Can. J. Chem. 1971, p. 2143 etseq.].

[0033] Suitable solvents are aromatic hydrocarbons such as toluene, o-,m- and p-xylene, ethers such as diethyl ether, diisopropyl ether,tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF),nitrites such as acetonitrile and propionitrile, and also dimethylsulfoxide, dimethylformamide and dimethylacetamide, especiallypreferably diethyl ether and THF. Mixtures of these may also be used.

[0034] Suitable bases are, generally, inorganic compounds such as alkalimetal hydrides and alkaline earth metal hydrides such as lithiumhydride, sodium hydride, potassium hydride and calcium hydride, alkalimetal amides such as lithium amide, sodium amide and potassium amide,organometal compounds, in particular alkali metal alkyls such asmethyllithium, butyllithium, and phenyllithium, alkali metal alkoxidesand alkaline earth metal alkoxides such as sodium methoxide, sodiumethoxide, potassium ethoxide, potassium tert-butoxide anddimethoxymagnesium. Sodium hydride and sodium methoxide are especiallypreferred.

[0035] In general, the bases are employed in catalytic amounts, but theymay also be used in equimolar amounts, in excess or, if appropriate, assolvent.

[0036] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ VIIIin an excess based on II.

[0037] Carboxylic esters of the formula III in which R¹ and R² areidentical and are Cl, F and CH₃ are hydrolyzed by customary methods togive the carboxylic acids of the formula IV [cf. Organikum [OrganicChemistry], 16th Edition, p. 415 and 622, VEB Deutscher Verlag derWissenschaften, Berlin 1985]. This reaction is usually carried out attemperatures from 10° C. to 80° C., preferably 20° C. to 60° C., in aninert organic solvent in the presence of a base such as alkali metalhydroxides or alkaline earth metal hydroxides, in particular sodiumhydroxide or potassium hydroxide.

[0038] Carboxylic acids of the formula IV can be amidated in the knownmanner directly with phenethylamines of the formula V to give thecompounds of the formula I [cf. Houben-Weyl, Methoden der OrganischenChemie, [Methods in Organic Chemistry], Vol. E5, pp. 941-972, GeorgThieme Verlag Stuttgart and New York 1985].

[0039] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ V inan excess based on IV.

[0040] Alternatively, carboxylic acids of the formula IV may first beactivated prior to amidation with V, for example by converting them intoacyl halides, in particular acyl chlorides of the formula IVa.

[0041] The chlorination of carboxylic acids IV is usually carried out attemperatures from −20° C. to 100° C., preferably −10° C. to 80° C., inan inert organic solvent [cf. Organikum, 16th Edition, p. 423 et seq.,VEB Deutscher Verlag der Wissenschaften, Berlin 1985].

[0042] Chlorinating agents which are suitable for this reaction are thecustomary inorganic or organic chlorinating agents, for example thionylchloride, oxalyl chloride, phosphorus trichloride, phosphoruspentachloride, phosphorus oxychloride, triphenylphosphine/CCl₄,preferably thionyl chloride.

[0043] Solvents which are suitable are aliphatic hydrocarbons such aspentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbonssuch as toluene, o-, m- and p-xylene, halogenated hydrocarbons such asmethylene chloride, chloroform and chlorobenzene, ethers such as diethylether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole andtetrahydrofuran, nitriles such as acetonitrile and propionitrile,ketones such as acetone, methyl ethyl ketone, diethyl ketone andtert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamideand dimethylacetamide, especially preferably acetonitrile, toluene andtetrahydrofuran. Mixtures of these may also be used.

[0044] In general, the chlorinating agents are employed in at leastequimolar amounts. It may be advantageous for the yield to employ themin an excess of up to 10 mol per mol of IV, preferably up to 5 mol, inparticular up to 3 mol.

[0045] The amidation of the acyl halides with the phenethylamine of theformula V is carried out as illustrated, for example, for the compoundIVa:

[0046] This reaction is usually carried out at temperatures of 0° C. to80° C., preferably 20° C. to 40° C., in an inert organic solvent in thepresence of a base [cf. Organikum, 16th Edition, p. 412 et seq., VEBDeutscher Verlag der Wissenschaften, Berlin 1985].

[0047] Suitable solvents are ethers such as diethyl ether, diisopropylether, tert-butyl methyl ether, dioxane, anisole and THF, nitrites suchas acetonitrile and propionitrile, and also dimethyl sulfoxide,dimethylformamide and dimethylacetamide, especially preferably diethylether and THF. Mixtures of these may also be used.

[0048] Bases which can be used are, generally, inorganic compounds suchas alkali metal carbonates and alkaline earth metal carbonates such aslithium carbonate, potassium carbonate and calcium carbonate, and alsoalkali metal hydrogen carbonates such as sodium hydrogen carbonate,furthermore organic bases, for example tertiary amines such astrimethylamine, triethylamine, tri-isopropylethylamine andN-methylpiperidine, pyridine, substituted pyridines such as collidine,lutidine and 4-dimethylaminopyridine, and bicyclic amines. Triethylamineand pyridine are especially preferred.

[0049] In general, the bases are employed in catalytic amounts, but theymay also be used in equimolar amounts, in excess or, if appropriate, assolvent.

[0050] In general, the starting materials are reacted with each other inequimolar amounts. It may be advantageous for the yield to employ V inan excess based on IVa.

[0051] The starting materials of the formula II which are required forthe preparation of the compounds I are known from the literature, forexample commercially available, or can be prepared via the followingroutes:

[0052] The bromination with N-bromosuccinimide (NBS) or1,3-dibromo-5,5-dimethylhydrantoin is usually carried out attemperatures of 0° C. to 200° C., preferably 20° C. to 110° C., in aninert organic solvent in the presence of a free-radical initiator [cf.Synthetic Reagents, Vol. 2, pp. 1-63, Wiley, New York (1974); J.Heterocyclic Chem. pp. 1431-1436 (1993); Synth. Commun. p. 2803 et seq.(1996); J. Med. Chem. p. 481 et seq. (1981)].

[0053] The bromine compounds IIb are oxidized directly to give α-ketoesters II. The oxidation with N-methylmorpholine oxide orp-dimethylaminopyridine oxide is usually carried out at temperatures of0° C. to 100° C., preferably 20° C. to 60° C., in dimethylsulfoxide [cf.Bull. Chem. Soc. Jpn., p. 2221 (1981)].

[0054] As an alternative, phenyl acetic esters IIa can also be oxidizeddirectly to give α-keto esters II. The oxidation can be carried out, forexample, with SeO₂ or KMnO₄; it is usually carried out at temperaturesof 20° C. to 180° C., preferably 20° C. to 120° C., in an inert organicsolvent [cf. Synthesis, p. 915 (1994); Synth Commun., p. 1253 (1988); J.Gen. Chem. USSR, Vol. 21, p. 694 et seq. (1951)].

[0055] The phenyl acetic esters Ia which are required for thepreparation of the compounds II are known from the literature orcommercially available.

[0056] Those specific compounds I which are not accessible by theabove-described routes can be prepared by derivatization of othercompounds I.

[0057] If the synthesis yields isomer mixtures, their separation is,however, generally not absolutely necessary since some of the individualisomers can be converted into each other during processing for use orupon use (for example when exposed to light, acids or bases).Corresponding conversions may also take place after application, forexample in the case of plant treatment in the treated plants or in thefungal or animal pests to be controlled.

[0058] The reaction mixtures are processed in the customary manner, forexample by mixing with water, phase separation and, if appropriate,chromatographic purification of the crude products. In some cases, theintermediate and end products are obtained in the form of colorless orpale brown, viscous oils which are freed or purified of volatilecomponents under reduced pressure and at moderately elevatedtemperature. If the intermediates and end products are obtained assolids, they can also be purified by recrystallization or digestion.

[0059] Collective terms which generally represent the followingsubstituents were used in the definitions of the symbols stated for theabove formulae:

[0060] halogen: fluorine, chlorine, bromine and iodine;

[0061] alkyl: saturated, straight-chain or branched hydrocarbon radicalshaving 1 to 4 carbon atoms, for example methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl;

[0062] haloalkyl: straight-chain or branched alkyl groups having 1 to 4carbon atoms (as mentioned above), it being possible for some or all ofthe hydrogen atoms in these groups to be replaced by halogen atoms asmentioned above, for example C₁-C₂-haloalkyl such as chloromethyl,bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

[0063] alkoxy: straight-chain or branched alkyl groups having 1 to 8carbon atoms (as mentioned above) which are bound to the skeleton via anoxygen atom (—O—);

[0064] haloalkoxy: straight-chain or branched haloalkyl groups having 1to 4 carbon atoms (as mentioned above) which are bound to the skeletonvia an oxygen atom (—O—);

[0065] Taking into consideration the intended use of thephenethylacrylamides of the formula I, the following meanings of thesubstituents, in each case alone or in combination, are especiallypreferred:

[0066] Those embodiments of the intermediates which are especiallypreferred with regard to the variables correspond to those of theradicals X_(m), Y_(n), R¹, R², R³, R⁴, R⁵ and R⁶ of the formula I.

[0067] Especially preferred compounds I are those in which R¹ and R² areidentical and are chlorine, fluorine or methyl.

[0068] Other compounds I which are especially preferred are those inwhich R¹ and R² are chlorine.

[0069] Likewise especially preferred compounds I are those in which R¹and R² are fluorine.

[0070] Especially preferred compounds I are furthermore those in whichR¹ and R² are methyl.

[0071] Other especially preferred compounds of the formula I are thosein which R¹ and R² are different, in particular those in which R¹ is abulkier radical than R².

[0072] Likewise especially preferred are compounds of the formula I inwhich R² is hydrogen.

[0073] Moreover, especially preferred compounds I are those in which mis 1 or 2 and X is in 3-, 4- or 3,4-position.

[0074] Other especially preferred compounds of the formula I are thosein which X_(m) is 3-C₁-C₄-alkoxy, 4-O—C(R^(a),R^(b))—C≡C—R^(c). Thesecompounds have the formula I′; in this formula, X′ is C_(l)-C₄-alkoxy.

[0075] Likewise especially preferred compounds I are those in which n is1 or 2 and Y is in the 3-, 4- or 3,4-position.

[0076] In addition, especially preferred compounds I are those in whichX is C₁-C₈-alkoxy and Y is halogen.

[0077] Moreover, compounds of the formula I which are especiallypreferred are those in which X is 3-methoxy.

[0078] Especially preferred compounds I are those in which R³ to R⁶ arehydrogen; these compounds correspond to the formula I.1:

[0079] Moreover, especially preferred compounds I are those in which R⁵and R⁶ are hydrogen; these compounds correspond to the formula I.2:

[0080] Likewise especially preferred compounds of the formula I.2 arethose in which R¹ and R² are in each case identical and are chlorine,fluorine or methyl, R³ and R⁴ are hydrogen or together form acyclopropyl ring, Y_(n) is in the 4-, 3,4- or 2,4-position and ischlorine, fluorine, methyl or ethyl, X is chlorine, fluorine,C₁-C₃-alkyl, C₁-C₃-alkoxy, benzyloxy, allyloxy, propargyloxy,trifluoromethoxy or difluoromethoxy and m is 1 or 2, wherein, if m is 2,X is in the 3,4-position.

[0081] Particularly preferred with regard to their use are the compoundsI which are compiled in the tables which follow. In addition, the groupsmentioned in the tables for a substituent are per se, independently ofthe combination in which they are mentioned, an especially preferredembodiment of the substituent in question.

[0082] Table 1

[0083] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-chloro and the radical X_(m) corresponds to one line of TableA for each compound.

[0084] Table 2

[0085] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0086] Table 3

[0087] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0088] Table 4

[0089] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-fluoro and the radical X_(m) corresponds to one line of TableA for each compound.

[0090] Table 5

[0091] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0092] Table 6

[0093] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0094] Table 7

[0095] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-CH₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0096] Table 8

[0097] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0098] Table 9

[0099] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0100] Table 10

[0101] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-CH₂CH₃ and the radical X_(m) corresponds to one line of TableA for each compound.

[0102] Table 11

[0103] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-(CH₂CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0104] Table 12

[0105] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-(CH₂CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0106] Table 13

[0107] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-CH(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0108] Table 14

[0109] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-C(CH₃)₃ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0110] Table 15

[0111] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-CF₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0112] Table 16

[0113] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0114] Table 17

[0115] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-(CF₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0116] Table 18

[0117] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-OCH₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0118] Table 19

[0119] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 3,4-(OCH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0120] Table 20

[0121] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 2,4-(OCH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0122] Table 21

[0123] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-OCF₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0124] Table 22

[0125] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-OCHF₂ and the radical X_(m) corresponds to one line of TableA for each compound.

[0126] Table 23

[0127] Compounds of the formula I.1 in which R¹ and R² are chlorine andY_(n) is 4-phenyl and the radical X_(m) corresponds to one line of TableA for each compound.

[0128] Table 24

[0129] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 4-chloro and the radical X_(m) corresponds to one line of TableA for each compound.

[0130] Table 25

[0131] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 3,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0132] Table 26

[0133] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 2,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0134] Table 27

[0135] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 4-fluoro and the radical X_(m) corresponds to one line of TableA for each compound.

[0136] Table 28

[0137] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 3,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0138] Table 29

[0139] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 2,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0140] Table 30

[0141] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 4-CH₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0142] Table 31

[0143] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0144] Table 32

[0145] Compounds of the formula I.1 in which R¹ and R² are fluorine andY_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0146] Table 33

[0147] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 4-chloro and the radical X_(m) corresponds to one line of TableA for each compound.

[0148] Table 34

[0149] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 3,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0150] Table 35

[0151] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 2,4-dichloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0152] Table 36

[0153] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 4-fluoro and the radical X_(m) corresponds to one line of TableA for each compound.

[0154] Table 37

[0155] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 3,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0156] Table 38

[0157] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 2,4-difluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0158] Table 39

[0159] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 4-CH₃ and the radical X_(m) corresponds to one line of Table Afor each compound.

[0160] Table 40

[0161] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0162] Table 41

[0163] Compounds of the formula I.1 in which R¹ and R² are methyl andY_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0164] Table 42

[0165] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 4-chloro and the radical X_(m) corresponds to oneline of Table A for each compound.

[0166] Table 43

[0167] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 3,4-dichloro and the radical X_(m) corresponds toone line of Table A for each compound.

[0168] Table 44

[0169] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 2,4-dichloro and the radical X_(m) corresponds toone line of Table A for each compound.

[0170] Table 45

[0171] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 4-fluoro and the radical X_(m) corresponds to oneline of Table A for each compound.

[0172] Table 46

[0173] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 3,4-difluoro and the radical X_(m) corresponds toone line of Table A for each compound.

[0174] Table 47

[0175] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 2,4-difluoro and the radical X_(m) corresponds toone line of Table A for each compound.

[0176] Table 48

[0177] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 4-CH₃ and the radical X_(m) corresponds to oneline of Table A for each compound.

[0178] Table 49

[0179] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0180] Table 50

[0181] Compounds of the formula I.1 in which R¹ is methyl, R² ishydrogen and Y_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0182] Table 51

[0183] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 4-chloro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0184] Table 52

[0185] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 3,4-dichloro and the radical X_(m) corresponds to one lineof Table A for each compound.

[0186] Table 53

[0187] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 2,4-dichloro and the radical X_(m) corresponds to one lineof Table A for each compound.

[0188] Table 54

[0189] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 4-fluoro and the radical X_(m) corresponds to one line ofTable A for each compound.

[0190] Table 55

[0191] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 3,4-difluoro and the radical X_(m) corresponds to one lineof Table A for each compound.

[0192] Table 56

[0193] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 2,4-difluoro and the radical X_(m) corresponds to one lineof Table A for each compound.

[0194] Table 57

[0195] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 4-CH₃ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0196] Table 58

[0197] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0198] Table 59

[0199] Compounds of the formula I.1 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds to one line ofTable A for each compound.

[0200] Table 60

[0201] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 4-chloro and the radical X_(m) corresponds to oneline of Table A for each compound.

[0202] Table 61

[0203] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 3,4-dichloro and the radical X_(m) corresponds toone line of Table A for each compound.

[0204] Table 62

[0205] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 2,4-dichloro and the radical X_(m) corresponds toone line of Table A for each compound.

[0206] Table 63

[0207] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 4-fluoro and the radical X_(m) corresponds to oneline of Table A for each compound.

[0208] Table 64

[0209] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 3,4-difluoro and the radical X_(m) corresponds toone line of Table A for each compound.

[0210] Table 65

[0211] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 2,4-difluoro and the radical X_(m) corresponds toone line of Table A for each compound.

[0212] Table 66

[0213] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 4-CH₃ and the radical X_(m) corresponds to oneline of Table A for each compound.

[0214] Table 67

[0215] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0216] Table 68

[0217] Compounds of the formula I.1 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0218] Table 69

[0219] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 4-chloro and the radical X_(m) corresponds toone line of Table A for each compound.

[0220] Table 70

[0221] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 3,4-dichloro and the radical X_(m) correspondsto one line of Table A for each compound.

[0222] Table 71

[0223] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 2,4-dichloro and the radical X_(m) correspondsto one line of Table A for each compound.

[0224] Table 72

[0225] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 4-fluoro and the radical X_(m) corresponds toone line of Table A for each compound.

[0226] Table 73

[0227] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 3,4-difluoro and the radical X_(m) correspondsto one line of Table A for each compound.

[0228] Table 74

[0229] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 2,4-difluoro and the radical X_(m) correspondsto one line of Table A for each compound.

[0230] Table 75

[0231] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 4-CH₃ and the radical X_(m) corresponds to oneline of Table A for each compound.

[0232] Table 76

[0233] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 3,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0234] Table 77

[0235] Compounds of the formula I.1 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 2,4-(CH₃)₂ and the radical X_(m) corresponds toone line of Table A for each compound.

[0236] Table 78

[0237] Compounds of the formula I.2 in which R¹ and R² are chlorine andY_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring and the radicalX_(m) corresponds to one line of Table A for each compound.

[0238] Table 79

[0239] Compounds of the formula I.2 in which R¹ and R² are fluorine andY_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring and the radicalX_(m) corresponds to one line of Table A for each compound.

[0240] Table 80

[0241] Compounds of the formula I.2 in which R¹ and R² are methyl andY_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring and the radicalX_(m) corresponds to one line of Table A for each compound.

[0242] Table 81

[0243] Compounds of the formula I.2 in which R¹ is methyl, R² ishydrogen and Y_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring andthe radical X_(m) corresponds to one line of Table A for each compound.

[0244] Table 82

[0245] Compounds of the formula I.2 in which R¹ is ethyl, R² is hydrogenand Y_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring and the radicalX_(m) corresponds to one line of Table A for each compound.

[0246] Table 83

[0247] Compounds of the formula I.2 in which R¹ is methoxy, R² ishydrogen and Y_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring andthe radical X_(m) corresponds to one line of Table A for each compound.

[0248] Table 84

[0249] Compounds of the formula I.2 in which R¹ is trifluoromethoxy, R²is hydrogen and Y_(n) is 4-chloro, R³ and R⁴ form a cyclopropyl ring andthe radical X_(m) corresponds to one line of Table A for each compound.TABLE A No. X_(m) A-1  2-Cl A-2  3-Cl A-3  4-Cl A-4  2-F A-5  3-F A-6 4-F A-7  2-CH₃ A-8  3-CH₃ A-9  4-CH₃ A-10 2-CH₂CH₃ A-11 3-CH₂CH₃ A-124-CH₂CH₃ A-13 3-CH₂CH₂CH₃ A-14 4-CH₂CH₂CH₃ A-15 3-CH(CH₃)₂ A-164-CH(CH₃)₂ A-17 2-OCH₃ A-18 3-OCH₃ A-19 4-OCH₃ A-20 2-OCH₂CH₃ A-213-OCH₂CH₃ A-22 4-OCH₂CH₃ A-23 3-OCH₂CH₂CH₃ A-24 4-OCH₂CH₂CH₃ A-253-OCH(CH₃)₂ A-26 4-OCH(CH₃)₂ A-27 2,3-(CH₃)₂ A-28 3,4-(CH₃)₂ A-293,5-(CH₃)₂ A-30 2,6-(CH₃)₂ A-31 2,3-(CH₂CH₃)₂ A-32 3,4-(CH₂CH₃)₂ A-333,5-(CH₂CH₃)₂ A-34 2,6-(CH₂CH₃)₂ A-35 3-CH₃, 4-CH₂CH₃ A-36 3-CH₂CH₃,4-CH₃ A-37 3-CH₃, 5-CH₂CH₃ A-38 2-CH₂CH₃, 6-CH₃ A-39 2,3-(OCH₃)₂ A-403,4-(OCH₃)₂ A-41 3,5-(OCH₃)₂ A-42 2,6-(OCH₃)₂ A-43 2,3-(OCH₂CH₃)₂ A-443,4-(OCH₂CH₃)₂ A-45 3,5-(OCH₂CH₃)₂ A-46 2,6-(OCH₂CH₃)₂ A-47 3-OCH₃,4-OCH₂CH₃ A-48 3-OCH₂CH₃, 4-OCH₃ A-49 3-OCH₃, 5-OCH₂CH₃ A-50 2-OCH₂CH₃,6-OCH₃ A-51 3-OCH₃, 4-OCH₂CH₂CH₃ A-52 3-OCH₂CH₂CH₃, 4-OCH₃ A-533-OCH₂CH₃, 4-OCH₂CH₂CH₃ A-54 3-OCH₂CH₂CH₃, 4-OCH₂CH₃ A-55 3-OCH₃,4-OCH(CH₃)₂ A-56 3-OCH(CH₃)₂, 4-OCH₃ A-57 3-OCH₃, 4-OCH₂—C₆H₅ A-583-OCH₂—C₆H₅, 4-OCH₃ A-59 3,4-(OCH₂—C₆H₅)₂ A-60 3-OCH₃, 4-OCH₂—CH═CH₂A-61 3-OCH₃, 4-OCH₂—C≡CH A-62 3-OCH₃, 4-OCH(CH₃)—C≡CH A-63 3-OCH₃,4-OCH(CH₃)—C≡C—CH₃ A-64 3-OCH₃, 4-OCH(CH₃)—C≡C—CH₂CH₃ A-65 3-OCH₃,4-OC(CH₃)₂—C≡CH A-66 3-OCH₃, 4-OC(CH₃)₂—C≡C—CH₃ A-67 3-OCH₃,4-OC(CH₃)₂—C≡C—CH₂CH₃ A-68 3-OCH₃, 4-OCH₂—C≡C—C₆H₅ A-69 3-OCH₃,4-OCH(CH₃)—C≡C—C₆H₅ A-70 3-OCH₃, 4-OC(CH₃)₂—C≡C—C₆H₅ A-71 3-OCH₃,4-OCH₂—C≡C-(4-Cl—C₆H₄) A-72 3-OCH₃, 4-OCH(CH₃)—C≡C-(4-Cl—C₆H₄) A-733-OCH₃, 4-OC(CH₃)₂—C≡C-(4-Cl—C₆H₄) A-74 3-OCH₃, 4-OCF₃ A-75 3-OCH₃,4-OCHF₂

[0250] The compounds I are suitable as fungicides. They aredistinguished by an outstanding activity against a broad spectrum ofphytopathogenic fungi, in particular from the classes of theAscomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some ofthe act systemically, and they can be employed in crop protection asfoliar- and soil-acting fungicides.

[0251] They are especially important for controlling a large number offungi on a variety of crop plants such as wheat, rye, barley, oats,rice, maize, grass, bananas, cotton, soya, coffee, sugar cane,grapevines, fruit species, ornamentals and vegetables such as cucumbers,beans, tomatoes, potatoes and cucurbits, and on the seeds of theseplants.

[0252] Specifically, they are suitable for controlling the followingplant diseases:

[0253] Alternaria species on vegetables and fruit,

[0254]Botrytis cinerea (gray mold) on strawberries, vegetables,ornamentals and grapevines,

[0255]Cercospora arachidicola on peanuts,

[0256]Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits

[0257]Erysiphe graminis (powdery mildew) on cereals,

[0258] Fusarium and Verticillium species on various plants,

[0259] Helminthosporium species on cereals,

[0260] Mycosphaerella species on bananas and peanuts,

[0261]Phytophthora infestans on potatoes and tomatoes,

[0262]Plasmopara viticola on grapevines,

[0263]Podosphaera leucotricha on apples,

[0264]Pseudocercosporella herpotrichoides on wheat and barley,

[0265] Pseudoperonospora species on hops and cucumbers,

[0266] Puccinia species on cereals,

[0267]Pyricularia oryzae on rice,

[0268] Rhizoctonia species on cotton, rice and lawns,

[0269]Septoria nodorum on wheat,

[0270]Uncinula necator on grapevines,

[0271] Ustilago species on cereals and sugar cane, and

[0272] Venturia species (scab) on apples and pears.

[0273] Moreover, the compounds I are suitable for controlling fungalpests such as Paecilomyces variotii in the protection of materials (e.g.wood, paper, paint dispersions, fibers and tissues) and in theprotection of stored products.

[0274] The compounds I are applied by treating the fungi, or the plants,seeds, materials or the soil to be protected against fungal infection,with a fungicidally active amount of the active ingredients. Applicationcan be effected both before and after infection of the materials, plantsor seeds by the fungi.

[0275] In general, the fungicidal compositions comprise between 0.1 and95, preferably between 0.5 and 90%, by weight of active ingredient.

[0276] When used in crop protection, the application rates are between0.01 and 2.0 kg of active ingredient per ha, depending on the nature ofthe desired effect.

[0277] In the treatment of seed, amounts of active ingredient of from0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required perkilogram of seed.

[0278] When used in the protection of materials or stored products, theapplication rate of active ingredient depends on the nature of the fieldof application and on the desired effect. Application rates which areconventionally used in the protection of materials are, for example,0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient percubic meter of material treated.

[0279] The compounds I can be converted into the customary formulations,e.g. solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The use form depends on the particular purpose; in any case,it should guarantee a fine and uniform distribution of the compoundaccording to the invention.

[0280] The formulations are prepared in a known manner, e.g. byextending the active ingredient with solvents and/or carriers, ifdesired using emulsifiers and dispersants, it also being possible to useother organic solvents as cosolvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol,butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethyl formamide) and water; carriers such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.highly-disperse silica, silicates); emulsifiers such as nonionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methyl cellulose.

[0281] Suitable surfactants are alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid, naphthalene sulfonic acid, phenolsulfonic acid, dibutylnaphthalene sulfonic acid, alkylaryl sulfonates,alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acidsand their alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof naphthalene sulfonic acid with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctylphenol,octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methyl cellulose.

[0282] Substances which are suitable for the preparation of directlysprayable solutions, emulsions, pastes or oil dispersions are mineraloil fractions of medium to high boiling point, such as kerosene ordiesel oil, furthermore coal tar oils and oils of vegetable and animalorigin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene,toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenesor their derivatives, methanol, ethanol, propanol, butanol, chloroform,carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene,isophorone, strongly polar solvents, e.g. dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and water.

[0283] Powders, materials for spreading and dusts can be prepared bymixing or grinding the active substances together with a solid carrier.

[0284] Granules, e.g. coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active ingredientsto solid carriers. Examples of solid carriers are mineral earths, suchas silica gel, silicas, silica gels [sic], silicates, talc, kaolin,attaclay, limestone, lime, chalk, bole, loess, clay, dolomite,diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide,ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammoniumphosphate, ammonium nitrate, ureas, and products of vegetable origin,such as cereal meal, tree bark meal, wood meal and nutshell meal,cellulose powders and other solid carriers.

[0285] In general, the formulations comprise from between 0.01 and 95%by weight, preferably between 0.1 and 90% by weight, of the activeingredient. The active ingredients are employed in a purity of from 90%to 100%, preferably from 95% to 100% (according to NMR spectrum).

Examples of Formulations are

[0286] I. 5 parts by weight of a compound according to the invention aremixed intimately with 95 parts by weight of finely divided kaolin. Thisgives a dust which comprises 5% by weight of the active ingredient.

[0287] II. 30 parts by weight of a compound according to the inventionare mixed intimately with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which has been sprayedonto the surface of this silica gel. This gives a formulation of theactive ingredient with good adhesion properties (active ingredientcontent 23% by weight).

[0288] III. 10 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 90 parts by weight of xylene, 6parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 molof oleic acid N-monoethanolamide, 2 parts by weight of calciumdodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol ofethylene oxide and 1 mol of castor oil (active ingredient content 9% byweight).

[0289] IV. 20 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 60 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight ofthe adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol ofcastor oil (active ingredient content 16% by weight).

[0290] V. 80 parts by weight of a compound according to the inventionare mixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill (active ingredient content 80% by weight).

[0291] VI. 90 parts by weight of a compound according to the inventionare mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which givesa solution which is suitable for use in the form of microdrops (activeingredient content 90% by weight).

[0292] VII. 20 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 40 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight ofthe adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol ofcastor oil. Pouring the solution into 100,000 parts by weight of waterand finely distributing it therein gives an aqueous dispersion whichcomprises 0.02% by weight of the active ingredient.

[0293] VIII. 20 parts by weight of a compound according to the inventionare mixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of the activeingredient.

[0294] The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, e.g. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orpouring. The use forms depend entirely on the intended purposes; in anycase, it is intended to guarantee the finest possible distribution ofthe active ingredients according to the invention.

[0295] Aqueous use forms can be prepared from emulsion concentrates,pastes or wettable powders (sprayable powders, oil dispersions) byadding water. To prepare emulsions, pastes or oil dispersions, thesubstances as such or dissolved in an oil or solvent, can be homogenizedin water by means of wetter, tackifier, dispersant or emulsifier.Alternatively, it is possible to prepare concentrates composed of activesubstance, wetter, tackifier, dispersant or emulsifier and, ifappropriate, solvent or oil, and such concentrates are suitable fordilution with water.

[0296] The active ingredient concentrations in the ready-to-usepreparations can be varied within substantial ranges. In general, theyare from 0.0001 to 10%, preferably from 0.01 to 1%.

[0297] The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even the activeingredient without additives.

[0298] Various types of oils, herbicides, fungicides, other pesticides,or bactericides may be added to the active ingredients, if appropriatealso only immediately prior to use (tank mix). These can be admixed withthe compositions according to the invention in a weight ratio of 1:10 to10:1.

[0299] In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,the [sic] eg. with herbicides, insecticides, growth regulators,fungicides or else with fertilizers. Mixing the compounds I or thecompositions comprising them in the use form as fungicides with otherfungicides frequently results in a broader fungicidal spectrum ofaction.

[0300] The following list of fungicides together with which thecompounds according to the invention can be used is intended toillustrate the possible combinations, but not to impose any limitation:

[0301] sulfur, dithiocarbamates and their derivatives, such as iron(III)dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfides [sic], ammonia complex of zinc(N,N-ethylenebisdithiocarbamate), ammonia complex of zinc(N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

[0302] nitro derivatives, such as dinitro(1-methylheptyl)phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitro-isophthalate;

[0303] heterocyclic substances, such as 2-heptadecyl-2-imidazolineacetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,2-(4-thiazolyl)benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide,

[0304] N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-di-methylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane;2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolyl-urea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4- triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)-oxiran-2-ylmethyl]-1H-1,2,4-triazole,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,

[0305] strobilurins such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate,methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide,methyl-E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,

[0306] anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,

[0307] phenylpyrroles such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,

[0308] cinnamamides such as3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholine,

[0309] and a variety of fungicides such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)-alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-(3,5-dichlorophenyl)5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,1-[2-(2,4-dichloro-phenyl)pentyl]-1H-1,2,4-triazole,2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

SYNTHESIS EXAMPLES

[0310] With due modification of the starting compounds, the protocolsshown in the synthesis examples below were used for obtaining furthercompounds I. The resulting compounds, together with physical data, arelisted in the table which follows.

Example 1 Preparation of Methyl 2-bromo-(4-Chlorophenyl)acetate

[0311] 116 g (0.585 mol) of 1,3-dibromo-5,5-dimethylhyntantoin [sic] and1 g of AIBN were added portionwise to the solution of 215.3 g (1.17 mol)of methyl 4-chlorophenylacetate in 500 ml of tetrachloromethane, and themixture was refluxed for 24 hours. This was followed by washing withwater and 1 N sodium hydroxide solution, the aqueous phases wereextracted with methylene chloride, and the organic phases were dried andconcentrated. This gave 260 g of the title compound.

[0312]¹H NMR [δ, (CDCl₃)]: 3.8 (s, 3H); 5.3 (s, 1H).

Example 2 Preparation of Methyl (4-Chlorophenyl)-2-oxoacetate

[0313] 97.2 g of a 75% strength aqueous N-methylmorpholine N-oxidesolution were added with ice-cooling to a solution of 100 g (0.38 mol)of the compound of Example 1 in 400 ml of dimethyl sulfoxide (DMSO).After the mixture had been stirred for 24 hours at 20 to 25° C., it waspoured into water and extracted with methyl tert-butyl ether (MtBE).After the organic phases had been dried, stripped from the solvent andchromatographed on silica gel (cyclohexane/MtBE [3:1]), 69 g of thetitle compound was obtained.

[0314]¹H NMR [δ, (CDCl₃)]: 4.0 (s, 3H); 7.5 (m, 2H) and 8.0 (m, 2H).

Example 3 Preparation of Methyl 3,3-dichloro-2-(4-Chlorophenyl)acrylate

[0315] A solution of 29.9 g (0.15 mol) of the keto ester of Example 2 in300 ml of acetonitrile were treated with 117.9 g of PPh₃ (0.45 mol), and69.3 g (0.45 mol) of carbon tetrachloride were then added dropwise.After the reaction solution had remained at approximately 56° C. for 4hours, it was concentrated; the residue obtained was chromatographedover silica gel with cyclohexane/MtBE (3:1). This gave 39.2 g of thetitle compound.

[0316]¹H NMR [δ, (CDCl₃)]: 3.8 (s, 3H); 7.3-7.4 (m, 4H).

Example 4 Preparation of 3,3-dichloro-2-(4-Chlorophenyl)acrylic Acid

[0317] A solution of 17.1 g (64 mmol) of the ester of Example 3 in 50 mlof methanol was treated with 193 ml of 1 N KOH solution and then stirredfor 20 hours at 20 to 25° C. After the solvent had been distilled off,the residue was acidified with 20% strength H₂SO₄ to pH 1 and extractedwith ethyl acetate. The organic phases were dried and stripped from thesolvent, whereupon 15 g of the title compound were isolated.

[0318]¹H NMR [δ, (CDCl₃)]: 7.25 (m, 2H); 7.40 (m, 2H) and 9.5 (s, 1H).

Example 5 Preparation of 3,3-dichloro-2-(4-Chlorophenyl)acryloylChloride

[0319] 35.5 g (0.298 mol) of thionyl chloride were added dropwise at 0°C. to the solution of 50 g (0.199 mol) of the acid of Example 4 in 200ml of diethyl ether and 23.6 g (0.298 mol) of pyridine. The solution wasstirred for 6 hours at 20 to 25° C. and then filtered. After the solventhad been distilled off, 42.1 g of the product were obtained, and thiswas reacted further without purification.

Example 6 Preparation of3,3-dichloro-2-(4-Chlorophenyl)-N-[2-(3,4-dimethoxy-phenyl)ethyl]acrylamide[I-1]

[0320]

[0321] A solution of 10.8 g (0.04 mol) of the acyl chloride prepared inExample 5 in 20 ml of methylene chloride was added dropwise to asolution of 7.24 g (0.04 mol) of homoveratrylamine and 4.04 g 25 (0.04mol) of triethylamine in 80 ml of methylene chloride. The solution wasstirred for 3 hours at 20 to 25° C., and washed with 3 N sodiumhydroxide solution and then with 10% by weight strength hydrochloricacid. The organic phase was freed from solvent, and 13.85 g of the titlecompound were obtained from the residue following chromatography onsilica gel with cyclohehane [sic]/MtBE (3:1).

[0322]¹H NMR [δ, (CDCl₃)]: 2.8 (m, 2H); 3.55 (m, 2H); 3.8 (s, 3H); 3.85(s, 3H); 5.6 (s, 1H); 6.60-6.80 (m, 3H); 7.25-7.40 (m, 4H).

Example 7 Preparation of 4-(2-Aminoethyl)-2-methoxyphenol

[0323]

[0324] 0.5 g of palladium on charcoal (10%) were added to 5 g (19.5mmol) of 2-[4-(benzyloxy)-3-methoxyphenyl]ethylamine [cf.: Heterocycles,Vol. 28, 297-298 (1989)] in 100 ml of tetrahydrofuran and the mixturewas hydrogenated under atmospheric pressure. After the uptake ofhydrogen had ended, the mixture was filtered and the filtrate was freedfrom the solvent.

[0325] The residue was triturated with diisopropyl ether, filtered anddried.

[0326] IR (cm⁻¹): 2935, 1593, 1515, 1263, 1230, 1032.

Example 8 Preparation of3,3-dichloro-2-(4-Chlorophenyl)-N-[2-(4-hydroxy-3-methoxyphenyl)ethyl]acrylamido-4-(2-aminoethyl)-2-methoxyphenol[I-52]

[0327]

[0328] 1 g of 4-(2-aminoethyl)-2-methoxyphenol, 2.21 g of1-benzotriazolyloxy-tris(dimethylamino)phosphonium hexafluorophosphate(BOP) and 1.5 g of N-ethyldiisopropylamine were added to 1.25 g of3,3-dichloro-2-(4-chlorophenyl)acryloyl chloride in 30 ml ofdimethylformamide (DMF), and stirring was continued for approximately 12hours at 23° C. The mixture was then treated with water and extractedwith ethyl acetate, and the extracts were washed with NaCl solution anddried. After the solvent had been removed, the residue waschromatographed over silica gel using cyclohexane/methyl tert-butylether (MtBE) (3:1). This gave the title compound in the form of an oil.

[0329] MS (m/e): M+H 400, 368, 366, 360.

Example 9 Preparation of3,3-dichloro-2-(4-Chlorophenyl)-N-[2-(4-hydroxy-3-methoxyphenyl)ethyl]acrylamide[I-53]

[0330]

[0331] 0.14 g of potassium carbonate and 0.12 g of propargyl bromidewere added to a solution of 0.4 g of3,3-dichloro-2-(4-chlorophenyl)-N-[2-(4-hydroxy-3-methoxyphenyl)-ethyl]acrylamidein 50 ml of DMF, the mixture was stirred for approximately 12 hours at23° C. After a further 0.14 g of potassium carbonate and 0.12 g ofpropargyl bromide had been added and the mixture had been stirred for afurther 6 hours at 23° C., the mixture was poured into water andextracted with MtBE, and the extracts were washed with water and dried.After removal of the solvent and chromatography on silica gel[cyclohexane/MtBE (1:1)], the title compound was obtained in the form ofan oil.

[0332]¹H-NMR (ppm): 2.5 (m, 1H); 2.8 (t, 2H); 3.6 (m, 2H); 3.8 (s, 3H);4.78 (s, 2H). TABLE I

Physical data (Mp. [° C.]; No. R¹ R² R³ R⁴ R⁵ R⁶ Y_(n) X_(m) ¹H NMR δ[ppm]) I-1 Cl Cl H H H H 4-Cl 3,4-(OCH₃)₂ 125-130 I-2 Cl Cl H H H H 4-Cl3-OCH₃, 4-OCH₂CH₃ 103-108 I-3 Cl Cl H H H H 4-Cl 2,3,4-(OCH₂CH₃)₃ 87-88I-4 Cl Cl H H H H 4-Cl 3,4-(OCH₂CH₃)₂ 111-121 I-5 Cl Cl H H H H 2-Cl3-OCH₃,4-OCH₂CH₃ 1.4(t); 2.8(m); 3.6(m); 3.8(s) I-6 Cl Cl H H H H 2-Cl3,4-(OCH₂CH₃)₂ 1.4(t); 2.7(m); 3.6(m); 4.0(s) I-7 Cl Cl H H H H 2-F3,4-(OCH₃)₂ 82-85 I-8 Cl Cl H H H H 2-F 3-OCH₃, 4-OCH₂CH₃  97-100 I-9 ClCl H H H H 2-F 3,4-(OCH₂CH₃)₂ 92-95 I-10 Cl Cl H H H H 3,4-Cl₂3,4-(OCH₃)₂ 124-127 I-11 Cl Cl H H H H 3,4-Cl₂ 3-OCH₃, 4-OCH₂CH₃ 110-113I-12 Cl Cl H H H H 3,4-Cl₂ 3,4-(OCH₂CH₃)₂ 115 I-13 Cl Cl H H H H 2,4-Cl₂3,4-(OCH₃)₂ 2.8(m); 3.6(m); 3.92(s); 3.95(s) I-14 Cl Cl H H H H 2,4-Cl₂3-OCH₃, 4-OCH₂CH₃ 1.4(t); 2.7(m); 3.5(m); 3.8(s) I-15 Cl Cl H CH(CH₃)2 HCH(CH₃)₂ 4-Cl 3,4-(OCH₃)₂ 157-160 I-16 CH₂CH₃ H H H H H 4-Cl 3,4-(OCH₃)₂1.0(t); 1.9(m); 2.8(t); 3.4(m) I-17 CH₂CH₃ H H H H H 4-Cl3-OCH_(3l , 4-OCH) ₂CH₃ 1.0(t); 1.5(t); 2.0(m); 2.7(t) I-18 CH₃ H H H HH 4-Cl 3,4-(OCH₃)₂ 1.6(d); 2.7(t); 3.5(m); 3.8(s) I-19 CH₃ H H H H H4-Cl 3-OCH₃, 4-OCH₂CH₃ 1.5(t); 1.6(d); 2.7(m); 3.5(m) I-20 CH₃ H H H H H4-F 3-OCH₃, 4-OCH₂CH₃ 1.5(t); 2.7(t); 3.3(m); 3.8(s) I-21 CH₃ H H H H H4-CF₃ 3-OCH₃, 4-OCH₂CH₃ 1.5(d); 1.6(t); 2.7(t); 3.5(m) I-22 CH₃ H H H HH 4-C(CH₃)₃ 3-OCH₃, 4-OCH₂CH₃ 1.3(s); 1.5(t); 1.7(d); 2.7(t) I-23 CH₂CH₃H H H H H H 3-OCH₃, 4-OCH₂CH₃ 1.0(t); 1.5(t); 2.0(m); 2.7(t) I-24 CH₂CH₃H H H H H 4-F 3-OCH₃, 4-OCH₂CH₃ 1.0(t); 1.5(t); 1.9(m); 2.7(m) I-25CH₂CH₃ H H H H H 4-CH₃ 3-OCH₃, 4-OCH₂CH₃ 1.0(t); 1.5(t); 2.0(m); 2.3(s)I-26 CH₂CH₃ H H H H H 4-CF₃ 3-OCH₃, OCH₂CH₃ 1.0(t); 1.5(t); 1.9(m);2.7(m); 3.5(m) I-27 CH₂CH₃ H H H H H 3,4-Cl₂ 3-OCH₃, 4-OCH₂CH₃ 1.0(m);1.5(m); 2.3(m); 2.8(t); 3.6(m) I-28 CH₂CH₃ H H H H H 2,4-Cl₂ 3-OCH₃,4-OCH₂CH₃ 1.1(t); 1.5(t); 2.6(m); 2.7(m); 3.5(m) I-29 CH₂CH₃ H H H H H3-CH₃ 3-OCH₃, 4-OCH₂CH₃ 1.0(t); 1.4(t); 2.7(t); 3.5(s); 3.8(s) I-30CH₂CH₃ H H H H H 2-F, 4-CH₃ 3-OCH₃, 4-OCH₂CH₃ 1.0(t); 1.5(t); 1.9(m);2.4(s); 2.7(t) I-31 CH₂CH₃ H H H H H 3,5-Cl₂ 3-OCH₃, 4-OCH₂CH₃ 1.0(t);1.4(m); 2.0(m); 2.7(t) I-32 H CH₂CH₃ H H H H 4-Cl 3-OCH₃, 4-OCH₂CH₃1.0(t); 1.4(t); 2.2(m); 3.7(m) I-33 Cl Cl H H H H 4-OCH₃ 3,4-(OCH₃)₂111-113 I-34 Cl Cl H H H H 4-OCH₃ 3-OCH₃, 4-OCH₂CH₃ 91-93 I-35 Cl Cl H HH H 4-OCH₃ 3,4-(OCH₂CH₃)₂ 128-129 I-36 Cl Cl H H H H 4-OCH₃ 3-OCH₂CH₃,4-OCH₃ 113-115 I-37 Cl Cl H H H H 3-CF₃ 3-OCH₃, 4-OCH₂CH₃ 2.8(t);3.5(m); 3.8(s); 3.9(s) I-38 Cl Cl H H H H 4-Cl 3-OCH₂CH₃, 4-OCH₃ 1.5(t);2.8(t); 3.6(m); 3.9(s); 4.0(m) I-39 Cl Cl H H H H 4-C(CH₃)₃ 3-OCH₃,4-OCH₂CH₃ 1.3(s); 1.5(t); 2.8(t); 3.5(m) I-40 Cl Cl H H H H 4-C(CH₃)₃3,4-(OCH₃)₂ 1.3(s); 2.8(t); 3.6(m); 3.8(s) I-41 Cl Cl H H H H 4-C(CH₃)₃3,4-(OCH₂CH₃)₂ 1.3(s); 1.6(t); 2.8(t); 3.6(m) I-42 Cl Cl H H H H 4-C₆H₅3-OCH₃, 4-OCH₂CH₃ 138-139 I-43 Cl Cl H H H H 4-C₆H₅ 3,4-(OCH₃)₂ 133-135I-44 Cl Cl H H H H 4-C₆H₅ 3,4-(OCH₂CH₃)₂ 124-125 I-45 Cl Cl H H H H4-C₆H₅ 3-OCH₃, 4-OCH₂CH₃   112-113.5 I-46 Cl Cl H H H H 4-Br 3,4-(OCH₃)₂124-126 I-47 Cl Cl H H H H 4-Br 3,4-(OCH₂CH₃)₂ 126-127 I-48 CH₃ CH₃ H HH H 4-Cl 3,4-(OCH₃)₂ 1.6(s); 2.1(s); 2.7(s); 3.6(s); 3.8(s) I-49 CH₃ CH₃H H H H 4-Cl 3-OCH₃, 4-OCH₂CH₃ 1.4(t); 2.1(s); 2.7(s); 3.6(s); 3.8(s)I-50 CH₃ CH₃ H H H H 4-Cl 3,4-(OCH₂CH₃)₂ 1.4(m); 1.7(s); 2.1(s); 2.7(s)I-51 OCH₃ H H H H H 4-Cl 3-OCH₃, 4-OCH₂CH₃ 95-98 I-52 Cl Cl H H H H 4-Cl3-OCH₃, 4-OH see Example 8 I-53 Cl Cl H H H H 4-Cl 3-OCH₃, 4-OCH₂C≡CHsee Example 9

Examples of the Action Against Fungal Pests

[0333] The fungicidal action of the compounds of the formula I wasdemonstrated by the following experiments:

[0334] The active ingredients were formulated separately or jointly as a10% strength emulsion in a mixture of 70% by weight of cyclohexanone,20% by weight of Nekanil® LN (Lutensol® AP6, wetter with emulsifying anddispersing action based on ethoxylated alkyl phenols) and 10% by weightof Wettol® EM (nonionic emulsifier based on ethoxylated castor oil) anddiluted with water to give the desired concentration.

[0335] Use Example 1—Efficacy Against Phytophthora Infestans on Tomatoes

[0336] Leaves of potted plants cv. “GroBe Fleischtomate St. Pierre” weresprayed to runoff point with an aqueous suspension made with a stocksolution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.The next day, the leaves were infected with a cold aqueous zoosporesuspension of Phytophthora infestans at a density [sic] of 0.25×10⁶spores/ml. Then, the plants were replaced into a chamber with 100%atmospheric humidity at temperatures between 18 and 20° C. After 6 days,the blight had developed to such an extent on the untreated, butinfected, control plants that it was possible to visually determine thedisease level in percent.

[0337] In this test, the plants which had been treated with 250 ppm ofthe active ingredients I-1, I-2, I-11, I-17, I-19, I-25, I-26, I-27,I-32, I-33, I-34, I-39, I-40, I-42, I-43, I-45, I-46 and I-49 of table Ishowed a disease level of not more than 10%, while the disease level ofthe untreated plants was 90%.

[0338] Use Example 2—Efficacy Against Plasmopara viticola

[0339] Leaves of potted grapevines of the variety “Müller-Thurgau” weresprayed to runoff point with an aqueous active ingredient preparationmade with a stock solution of 10% active ingredient, 63% cyclohexanoneand 27% emulsifier. The next day, the leaves were inoculated with anaqueous zoospore suspension of Plasmopara viticola. Then, the grapevineswere first placed for 48 hours into a chamber at 24° C. and 100%atmospheric humidity and then for 5 days in a greenhouse at temperaturesbetween 20 and 30° C. After this time, the plants were returned for 16hours into a humid chamber to accelerate the eruption ofsporangiophores. The extent to which the disease had developed on theundersides of the leaves was then determined visually.

[0340] In this test, the plants which had been treated with 250 ppm ofthe active ingredients I-1, I-2, I-10, I-11, I-12, I-16, I-17, I-19,I-21 to I-27, I-29, I-30, I-32, I-33, I-34, I-39, I-40, I-42, I-43,I-45, I-46, I-48 and I-49 of table I showed a disease level of not morethan 10%, while the disease level of the untreated plants was 90%.

[0341] Comparative Experiment—Long-term Action Against Phytophthorainfestans on Tomatoes

[0342] Tomato plants cv. “Groβe Fleischtomate St. Pierre” in the 4-leafstage were sprayed to run off point with an aqueous suspension made witha stock solution of 10% active ingredient, 63% cyclohexanone and 27%emulsifier. To test the long-term action of the compounds, the leaveswere infected with an aqueous zoospore suspension of Phytophthorainfestans one week after application. The plants were subsequentlyplaced in a chamber with 100% atmospheric humidity at temperaturesbetween 16 and 18° C. After 6 days, the blight had developed to such anextent on the untreated, but infected, control plants that it waspossible to visually determine the disease level in %.

[0343] The compound of the structure below, which is known from WO-A96/23763, acted as comparative active ingredient:

[0344] In this test, the plants which had been treated with 63 ppm ofthe active ingredients I-1, I-2, I-11, I-33 and I-34 of table I showed adisease level of zero to 25%, while the plants which had been treatedwith 63 ppm of the comparative active ingredient showed a disease levelof 40% and the untreated plants showed a disease level of 100%.

We claim:
 1. The use of phenethylacrylamides of the formula I

in which the substituents have the following meanings: X is halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy, C₁-C₄-haloalkoxy and—O—C(R^(a),R^(b))—C≡C—R^(c); R^(a),R^(b) independently of one anotherare hydrogen and C₁-C₆-alkyl; R^(c) is hydrogen, C₁-C₈-alkyl,C₃-C₈-cycloalkyl and phenyl which can be substituted by halogen, cyano,nitro, CF₃, C₁-C₄-alkyl and/or C₁-C₄-alkoxy; m,n independently of oneanother are 1 to 4, it being possible for the radicals X and Y to bedifferent if m or n is greater than 1; Y is halogen, nitro, cyano,C₁-C₄-alkyl, CF₃, C₁-C₄-alkoxy and phenyl; R¹, R² independently of oneanother are hydrogen, halogen, C_(l)-C₄-alkyl, C_(l)-C₄-alkoxy,C_(l)-C₄-haloalkoxy and CF₃; R³,R⁴,R⁵,R⁶ independently of one anotherare hydrogen, C₁-C₄-alkyl and C₁-C₄-alkoxy or R³ and R⁴ together form acyclopropyl ring, it being possible for the C—R⁵- and C—R⁶-bonds to bein the E- or Z-position relative to each other; for controllingphytopathogenic fungal pests.
 2. A phenethylacrylamide of the formula Ias claimed in claim 1 wherein R¹ and R² are identical and are Cl, F andCH₃.
 3. A phenethylacrylamide of the formula I as claimed in claim 1 or2 where m is 1 or 2 and X is in the 3-, 4- or 3,4-position.
 4. Aphenethylacrylamide of the formula I as claimed in any of claims 1 to 3where n is 1 or 2 and Y is in the 3-, 4- or 3,4-position.
 5. Aphenethylacrylamide of the formula I as claimed in any of claims 1 to 4where X is C₁-C₈-alkoxy and Y is halogen.
 6. A phenethylacrylamide ofthe formula I as claimed in any of claims 1 to 5 where R³ and R⁴ arehydrogen.
 7. A phenethylacrylamide of the formulae


8. A process for the preparation of a compound of claims 2 to 7, whichcomprises [lacuna] α-keto esters of the formula II,

where R is C₁-C₄-alkyl with triphenylphosphine and, if R¹ and R² arechlorine, with CCl₄, or, if R¹ and R² are fluorine, with sodiumdifluorochloroacetate, or, if R¹ and R² are methyl, withisopropyltriphenylphosphonium halide under basic conditions to giveacrylic esters of the formula III

and hydrolyzing III to give carboxylic acids of the formula IV

and subjecting IV to a condensation reaction with phenethylamines of theformula V

to give compounds of the formula I.
 9. A composition which is suitablefor controlling phytopathogenic harmful fungi, comprising a solid orliquid carrier and a compound of the formula I as claimed in any ofclaims 2 to
 7. 10. The use of the compound I as claimed in any of claims2 to 7 for preparing a composition which is suitable for controllingphytopathogenic harmful fungi.
 11. A method of controllingphytopathogenic harmful fungi, which comprises treating the fungi or thematerials, plants, the soil or seed to be protected from fungalinfection with an effective amount of a compound of the formula I asclaimed in any of claims 1 to 7.